Mordant treating process and elements containing same



mordant.

No Drawing. Filed June 19, 1956, Ser. No. 592,245 6 Claims. (Cl. 96-77) This invention relates to photography and more particularly to a process for improving photographic polymeric acid dye mordants useful in dye imbibition or dye transfer printing elements. Still more particularly, it relates to film elements containing improved polymeric acid dye mordants. More specifically, this invention relates to photographic silver halide emulsions containing polymeric acid dye mordants which have been admixed in solution with polyvalent metal ions. The invention further relates to a process for reducing the back transfer properties of metal ion-mordant solutions by aging and to water-permeable colloid emulsions and film elements containing the resultant solutions.

It is well known that the dye mordant used in mordanted films in dye imbibition or dye transfer printing operations tends to diffuse out of the mordanted image receiving element and into the image bearing gelatin matrix. This migrating or diffusion of the mordant is called back transfer and is highly objectionable in dye imbibition or dye transfer printing. Specially, upon repeated transfer of successive dye applications from the same matrix in routine printing operations, the matrix becomes infused with dye mordant, accumulated from the premordanted image receiving element with each successive printing, and the efficiency and usefulness of the matrix is thus impaired. In addition, the dye mordant may typically spread into the areas of the matrix which should not contain the transfer dye and thus ultimately cause lack of sharpness and objectionable dye density in highlight areas of the final print.

An object of this invention is to provide a process for improving the back transfer properties of a photographic acid dye mordant. A further object is to provide a process for treating acid dye mordants which results in reduction in the amount of back transfer of the mordant during dye imbibition or dye transfer printing. A still further object is to provide such a process for treating a polymeric mordant for inclusion in a dye print receiving film element, and particularly in a light-sensitive silver halide photographic emulsion without causing any deleterious effect to either the emulsion or the polymeric Another object is to provide such a process for obtaining improved dye mordants which exhibit reduced back transfer and do not harmfully afiect the photographic properties of the emulsion, such as sensitometric gamma, fog and fog stability.

An additionalobject of-this invention is to provide improved film elements,'including gelatin blanks, light-sensitive silver'halide emulsions and photographic filmshaving light-sensitive layers, which elements contain polymeric acid dye mordants which exhibit negligible back transfer when used in dye imbibition or dye transfer processes. Yet another object is to provide suchmordanted elements in which mordanted acid dy-e images of good resolution may be formed. A further and more specific object of the invention is to provide photographic silver halide emulsions which contain non-fogging polymericacid dye mordants which have been admixed in aqueous solution with polyvalent metal ions. A still further object is to provide such emulsions containing such metal ion-treated mordants which are non-diffusing in water-permeable colloid layers and have'no deleterious action onlight- I Patented Jan. 29, 1%33 sensitive silver halides. Still other objects will be apparent from the following description of the invention.

It has been found that a decrease in back transfer of dye mordant in dye transfer processes results when a polymeric acid dye mordant is used in the image receiving film element in the dye transfer printing operation, which mordant has been treated by admixing the mordant in solution with polyvalent metal ions each having a valence of two or more. The undesired characteristics of 'back transfer are further markedly decreased if the treated mordant is given an aging treatment as described below prior to inclusion of the mordant in the water-permeable colloid, e.g., gelatin, hinder, the coated layer of which is to ultmiately receive the transfer dye. The invention in its broadest aspects comprises a process for reducing the diffusing or back transfer tendencies of a polymeric acid dye mordant of the type having recurring extralinear amino groups by admixing the mordant, prior to inclusion in the image receiving element, in solution with polyvalent positive metal ions each having a valence of two or more, said metal ions being present in an amount of at least 0.006 mol per grams of mordant present. The metal ions may conveniently be introduced by adding a corresponding metal salt to a solution already containing the mordant, or by adding the mordant to a solution of the metal salt, or by admixing two separate solutions, one of which contains the mordant and the other of which contains the metal ions which may have been introduced as a metal salt. After mixing, the mordant-metal ion solution can then be added to a water-permeable colloid binder for making a film element.

In a more specific aspect, the invention comprises a process for reducing the diffusing or back transfer tendencies of a polymeric mordant for acid dyestuffs, said mordant being of the type having recurring extralinear amino groups, which process comprises mixing the mordant, prior to inclusion in the image receiving element, in solution with polyvalent positive metal ions each having a valence of 2 or more, said metal ions being present in an amount of at least 0.006 mol per 100 grams of mordant present, followed by an aging step. The aging step comprises subjecting the solution to certain conditions of time and temperature which can be varied over wide limits to suit the particular conditions. it has been found that suitable aging with its subsequent reduction in back transfer can even be carried out at refrigeration temperatures of about 45 F. if the aging period is allowed to take place for a sufficiently long time. Temperatures as low as 32 F. and as high as 212 F. are considered satisfactory. Further, there is no required minimum or maximum period of time necessary for aging of the mordant-metal ion solution; the longer the aging period, the greater the reduction of back transfer. For example, an approximately equal reduction in back transfer occurs by carrying out the aging proces for 264 hours at 45 R, 48 hours at 95 F. fo r 2 /2 hours at F. More or less aging treatment at any given temperature results respectively in a higher or lower degree of improvement in back transfer reduction.

The invention also comprises the ,Water permeable able support or layer to make a film element, which m ay be used as the image receptive element in adye imbibition transfer process.

1; t2) In a prefered embodiment of this invention, a photographic emulsion can be made by simply mixing the mordant treated according to the above described processes of this invention with an aqueous dispersion or emulsion of light-sensitive silver halide in a water-permeable colloid, which may contain the usual emulsion adjuvants, e.g., sensitizing dyes, stabilizers, hardeners, anti-foggants, etc., prior to coating onto a suitable support or layer to form a photographic element. in general, the amount of mordant used is about 25 to 55 grams per mol of silver halide. The resulting products have excellent mordanting properties with respect to acid dyes, and are particularly distinguishable by the superior non-diffusing properties of the polymeric mordant.

The polymeric mordants within the scope of this invention include polymeric acid dye mordants having recurring extralinear amino groups. By amino groups we mean either an amino group itself or an acid salt or quaternary salt thereof. The polymers may be substituted or unsubstituted and may include polymers of amines, amine acid salts and quaternary ammonium salts, and copolyrners of two or more said amines, amine acid salts and quaternary ammonium salts with each other or with other polymerizable ethylenically unsaturated compounds in an amount not exceeding about 50% of the latter. Preferably, the polymeric mordants of this invention are selected from the group consisting of (a) vinyl copolymers of monoethylenically unsaturated compounds having tertiary amine salt groups and monoethylenically unsaturated compounds having quaternary ammonium salt groups, (1;) vinyl copolymers of said unsaturated compounds with up to 50% by weight of another monoethylenically unsaturated compound, and (c) quaternary salts of polyvinylyridine. Suitable polymeric mordants for the processes and products of this invention include the polymeric polyamine mordants disclosed in Gray U.S. application Serial No. 379,467, filed September 10, 1953, now US. Patent 2,753,263, issued Euly 3, 1956, the quaternary salt products of polyvinylpyridine disclosed in Minsk et al. US. Patent No. 2,484,420, and the alkyl amine polymers disclosed in Carroll et al. US. Patent No. 2,675,316. The especially preferred mordants are the copolymeric alpha-alkacrylic acid esters of amino alcohols having tertiary and quaternary salt groups in the proportion of 35 to 75 mol percent of the former to 65 to 25 mol percent of the latter, which are disclosed in Gray and Webers U.S. application Serial No. 478,544, filed December 29, 1954-, now U.S. Patent 2,839,401, issued June 17, 1958. lolymeric moi-dents having molecular weights above 10,000 are preferred.

The metal ions useful in this invention include those which are well known in the photographic art as gelatin hardening agents. Such hardening or cross-linking of gelatin or other proteinaceous material is well known. Suitable metal ions which may be introduced, as stated above, in the form of an appropriate ionizable salt include chromic, cupric, aluminum and ferric ions. Suitable salts containing suitable metal ions include chromic bromide, chromic sulfate, aluminum chloride, potassium aluminum sulfate, ferric chloride, ferric sulfate, ferric ammonium sulfate, cupric chloride, cupric sulfate, etc. Of the useful salts, those which contain ionizable trivalent metal ions are preferred, and, in particular, the preferred metal salt is chrome alum.

It has been found that the range of concentration of metal ions, when used in the processes and products of this invention, is limited to a minimum amount of at least about 0.006 mol per 100 grams of mordant present. It has been found that below the stated range the amount of metal ion added is insufficient to eiiect any significant improvement in the back transfer properties of the mordant. The upper limit is not as critical but it has been found that larger amounts of metal ions cause brittleness of the water-permeable colloid emulsion or film product. The upper limit will therefore be determined by the amount of brittleness which can be tolerated in the film product, and brittleness is also affected by other factors, e.g., emulsion additives and ambient conditions of temperature and humidity. Metal ions in an amount as great as 0.085 mol and more per grams of mordant are considered satisfactory. The preferred range of iron concentration is from 0.02 to 0.055 mol per 100 grams of mordant.

Surprisingly, it has been found that it is essential to admin the metal ions with the polymeric mordant prior to the inclusion of the mordant in the photographic emulsion or film element. Mere addition of the metal ions to the photographic emulsion, or to the water-permeable colloid as is done when the ions are used as colloid hardening agents does not attain the outstanding improvement in reduction or" the diffusion tendencies of dye mordants.

The colloids used as the binders in the emulsions ac cording to this invention may be of any of the usual colloids used by photographic manufacturers. They are generally water-permeable and may be of natural or synthetic composition. Thus, the colloid, which is preferably gelatin, may be agar-agar, albumin, zein, collodion, polyvinyl alcohol, partly hydrolized polymeric acetals, and hydrophilic copolymers thereof with ethylenically unsaturated monomers such as ethylene, vinl chloride, etc; polyvinyl acetals, e.g., the acetals of polyvinyl alcohols with acetaldehyde or benzaldehyde; or water soluble or hydrophilic cellulose derivatives. Suitable binders or water-permeable colloids of the above types are described in US. Patents Nos. 2,110,491, 2,211,323, 2,276,322, 2,276,323, 2,286,215 and 2,397,866.

To form a film element, which may be done according to well known means, the emulsion containing the metal ion-mordant solution according to this invention is coated on a suitable support. Such supports include paper, which may be baryta coated, cardboard, or water proofed or transparentized paper or other film. The support may be composed of any suitable hydrophilic sheet or pellicle, e.g., cellulose derivatives such as cellulose nitrate, cellulose triacetate, cellulose proprionate, cellulose acetate butyrate; polyvinyl chloride, polyvinyl chloride/ acetate; hydrophilic acetals, e.g., from formaldehyde and acetaldehydes, superpolymers, e.g., polyamides, polyesters such as polyethylene terephthalate, polystyrene, etc. The film supports may be clear or may contain dyes or pigments. The coated polyester film base described in Alles and Saner US. Patent No. 2,627,- 088 is especially useful as a support material.

In admixing the polymeric mordant with the metal ions in a solution, the solvent must be a common solvent for both the mordant and the metallic salt. Pmticularly when the usual water-permeable colloids listed above are used as a binding material, the solvent is typically and preferably water.

The processes and products further described but are not the following examples.

EXAMPLE I A washed positive-type light-sensitive lode-bromide gelatin photographic emulsion was given a customary second digestion treatment and divided into four equal parts. To the first part was added a 5% aqueous solution of diethylaminoethylmethacrylate tertiary salt-diethylaminoethylmethacrylate quaternary salt copolymer having a mol ratio of 60% tertiary salt to 40% quaternary salt copolymer made according to the procedures described in Gray et al. application Serial No. 574,593, filed March 29, 1956, in the amount of 22.0 grams of copolymer per 100 grams of emulsion gelatin. To the second part of the emulsion there was added an equal amount of copolymer mordant solution which had been aged at F. for 21 hours. To third part of the emulsion there was added an equal of this invention will be intended to be limited by amount of copolymer mordant solution to whichhad been part of emulsion was added an equal amount of polymer mordant-chrome alum mixture as in part three, except the mixture was aged at 140 F. for 21 hours prior to use. To emulsion portions one and two there was then added an amount of chrome alum which was equal to that contained in the mordant-chrome alum mixtures used in portions three and four. The usual post-digestion additives of stabilizers, coating aids, etc., were added to each portion and the emulsions were coated on a thin cellulose acetate film support and dried in the customary manner.

Sample strips of each coating were then processed without exposure in a positive-type metol-hydroquinone developing solution and fixed in a non-hardening type hypo fixing bath to eliminate the silver halide.

The film samples were then dried and tested by an imbibition transfer procedure for the degree of mordant migration which approximates the level of mordant back transfer that normally accrues during the commercial operation from successive dye imbibition transfers from a Single matrix. The aqueous dye solution used was adjusted to a pH of 2.4 to 3.0 and contained approximately 1.6 grams of Pontacyl Carmine 6B Extra Concentrated (Colour Index No. 57) magenta dyestuit per liter of water. The spectral density of residual dye stain on the film used to test the level of back transfer was read on a color densitometer (as described in J.S.M.P.T.E., 56, page 23. 1951) at a wavelength of 540 millimicrons. The spectral density of such residual dye stain is a direct measure of the degree of back transfer. The greater the amount of mordant adsorbed from the mordanted blank during the imbibition transfer test, the greater is the density of residual stain. For example, it a control film containing no mordant is used in place of the mordanted film in the test procedure described above, the spectral density of residual dye stain as read at a wavelength of 540 millimicrons is zero to within the accuracy of the density determination.

Sensitometric testing of the four light sensitive silver halide emulsion coatings containing the mordants which had been variously treated as described above was carried out as follows: Samples of each coating were given a Ib sensitometric exposure and developed for 3 /2 minutes in a positive-type metol-hydroquinone developer at 68 F. Fixing, washing, drying and determination of speed, gamma, and fog were carried out in the customary manner. Duplicate samples of each coating were subjected to an incubation treatment at a temperature of 120 F. and 65% relative humidity for 48 hours and processed together with the non-incubated samples. For the incubated samples, only the fog values were recorded. The data are given in Table I.

Table 1 Density Fresh test Incu- Ccat- Mordant of bated iug treatment residual test No. dye Speed Gamma Fog Fog stain 1.. None 1.26 100 3. 07 .01 13 2 Aged 21 hrs. at 140 1.19 102 3. 23 .01 13 F. Without chrome alum. 3 Aged 21 hrs. at, 75 .77 100 3.18 .01 .10

F. with chrome alum. 4 Aged 21 hrs. at 140 .06 06 3.18 .01 .06

F. with chrome alum.

The results of Example I show that the process of metal ion treatment and aging, as in coating Nos. 3 and 4, gives a reduction in back transfer of, respectively, about 38.9% and 95.2% over the untreated mordant. There has been no deleterious aifect on the photographic properties of the emulsion. The slight indicated reduction in speed is not critical in positive type emulsions and can be compensated for by means well known in the art.

EXAMPLE n In this example the reduction of back transfer as a function of variation of the aging time of polymeric mordant-metal ion mixtures at elevated temperature is illustrated. To a 5% aqueous solution of diethylaminoethylmethacrylate tertiary salt-diethylaminoethylmethacrylate quaternary salt copolymer mordant was added chrome alum as described in Example I. The copolymeric mordant-chrome alum mixture was divided into seven equal parts and each portion was subjected to the aging treatment indicated in Table II. A washed positive-type lightsensitive iodo-bromide gelatin photographic emulsion was divided into seven equal portions after the customary second digestion treatment. To each portion of emulsion was then added one of the pro-aged mordant-chrome alum mixtures. The quantities of various ingredients were so calculated that after combination each emulsion portion contained 22.0 grams of copolymer per 100 grams of emulsion gelatin and 0.041 mol of chrome alum per 100 grams of mordant. Equal quantities of the usual post digestion adjuvants were added to each emulsion portion and the emulsions were then coated and dried. Samples of each coating were then tested for back transfer, and

sensitometric speed, gamma, and fog as described in Example I. The mordant-chrome alum mixture pre-treatment and the results of the tests are given in Table II.

Table II Density Fresh test Incu- Ooat- Mordant of bated ing treatment residual test No. dye Speed Gamma Fog Fog stam 1 21 hrs. at 75 44 2. 86 .02 09 2 15 Min. at F.+ 33 96 3. 04 .02 07 20% hrs. at 75 F. 3 1 hr. at 140 F. plus 15 75 2.97 .02 .08

20 hrs. at 75 F. 4 2% hrs. at 140 F. .08 68 3.26 02 11 plus 18% hrs. at 75 F. 5 5 hrs. at 140 F. .06 68 2. 97 .02 .16

plus 16 hrs. at 75 F. 0 10 hrs. at 140 F. .05 64 3.00 .02 .10 a plus 11 hrs. at

75 F. '7"-.. 21 hrs. at 140 F.-- .05 66 2. 93 02 .;11

EXAMPLE III .Thisexample serves to illustrate the effect of varying both the time and the temperature of mordant-metal ion solution aging treatment as a means of reducing the undesirable eiiects of back transfer during imbibition dye transfer printing operation.

To seven equal quantities of the tertiary-quaternary copolymeric mordant compositions previously described in Examples I and H were added equal amounts of chrome alum at proper time intervals so that the varying aging treatments noted in Table III could be carried out immediately in -advance of the emulsionpreparation,coating and drying operations. A washed positive-type lightsensitive iodo-bromide gelatin photographic emulsion was given a customary second digestion treatment and divided into seven equal portions. One or" the pro-aged mixed at such times that aging at varying time and temperature conditions as outlined in Table 1V were com pleted immediately before the carrying out of the final emulsion preparation. One of the above pretreated morpolymeric mordant-chrome alum mixtures Was added to 5 dant-chrorne alum mixtures was then added to a portion each of the emulsion portions. The quantities of ingrediof washed positive-type light-sensitive iodo-bromide gelaents were such that each of the final emulsion portions tin photographic emulsion which had been given a cuscontained 22.0 grams of copolymeric mordant per 100 tomary second digestion treatment. The remaining opergrams of gelatin and 0.041 mol of chrome alum per 100 ations of addition of post-digestion adjuvants, coating, grams of mordant. After addition of the usual post di- 10 drying, test for back transfer, sensitometric test, etc., gestion adjuvants, the seven emulsions were coated and were carried out as described in the preceding Examples. dried in a manner similar to that employed in Examples The concentrations of chrome alum employed, the condi- I and H. Samples of each coating were then tested for tions of the aging treatment, the nature of the mordantback transfer and sensitometric values as described in chrome alum mixture treatment and the results of the Example 1. Details of the mordant-chrome alum mix- 5 etsts are presented in Table IV.

Table IV Mols t Density Fresh test Coating Chrome Moment-chrome of re- Inc N o. alum per alum treatment sidual ba- 100 g. of dye stain tion mordant Speed Gamma Fog test 0. 041 24hr .at 80 F .42 100 3.27 .02 .10 0.0015 24 hrs. at 80F .32 as 3.30 .01 .10 0. 041 24hrs.at 95F .14 84 3.13 .01 .10 0.0015 24 hrs. at 95F .12 07 2. s7 .01 .01 0 041 48 hl'S. at F .00 67 3. 0s .01 .00 0. 0015 48 hrs. at 95 11- .00 00 2. 77 .01 .05 0. 041 11 days at 45 72 3.17 .01 .07

ture aging used in each case and results of the tests are It can be seen from the data in Table IV that variashown in Table III. tion in the amount of chrome alum present in the Table HI polymeric mordant-chrome alum mixture within the range of the invention does not markedly aifect the efiicacy of the aging treatment. It is also apparent that Dmsitv of Fresh test a sizable reduction in back transfer can be accomplished Coating N0. Mordantehrome residual by carrying out the polymeric mordant-metal ion mixalum treatment dye 5mm Speed Gamma Fag ture aging treatment of the invention even at temperatures substantially below ordinary room conditions as Fresh solutions 0. 57 100 3 2s .02 well as at elevated temperatures as described in this and 0.56 105 3.37 .02 th v 1 O 23 95 3'41 1n e prece mg eaamp es. 0122 00 3.34 .01 0.20 82 3.27 .01 EXAMPLE V a a A 5% aqueous solution of diethylaminoethylmethaca rylate tertiary salt-diethylaminoethylmethacrylate qua- It can be seen from the data presented in Table Ill that ternary Salt copolymer.n?odra.nt as dfiscnbed Example .c .1 I was prepared and divided into 8 equal portions. To one days aging treatment or the polymeric mordant- N 1 nddod n 041 1 f h 1 A chrome alum mixture at 95 F. eficcts the same reduction pogwn was mo 0 C in back transfer as would occur for approximately three 10 f P 3 was a e days aging at 75 F. It is also evident from the data H101 of potassfml aluminum Sulfate P 100 of that 4 days aging tmatment at is superimto 5 dant; to portion No. 5 was added 0.041 mol of ferric days aging treatment at 75 F. insofar as reduction in ammOml-Im Sulfate p 190 of mofdant, and t0 Portion back transfer is concerned. No. 7 was added 0.041 mol of cupric sulfate per 100 g. of mordant. Portions numbered 1 3 5 and 7 were then v V EAAMPLIE I aged for 24 hours at 140 F. The remaining mordant In this example illustration is made that reduction 1n portions b d 2, 4, 6 and 8 were kept at 75 F. b transfer y f agmgfifefiltmem of Polymeric without further addition or treatment. After a customary dam and metal Ion combinations also be egected second digestion, a Washed positive-type light-sensitive 7 1 by the p; tfimpemmre; l i or 69 iodobromlde gelatln photographic emulsion was divlded p condltlons C i 5 ii i g into eight equal portions and one of the eight mordant firatlonpsystegli Y gi f g gg k compositions variously treated as described above was peraturis y a l l combined with one of the emulsion portions. To emullliustration is also made that metal ion concentrations I sion-mordant admixture No. 2 was then added the same other than those used in the preceding examples will serve equally Wen. quantity of chrome alum as had PTBVIOUSLY been em- Amounts of chrome alum were added to seven equal Ployed the: mordarft'chmme gi treat quantities of the tertiary-quaternary copolymer mordant want 9 min-dam Portion mmuarly i molar solutions as set forth in Examole I such that the concenquantifies of Petassmm aluminum Sulfate fsmc ammo tion of hr me alum in th fin l photographic m- 70 nium sulfate, and cupric sulfate were added to emulsionsion composition would correspond as indicated in Table mofdam 36111115111"? P and 8 p w e y- The rv to either 0.041 mol or 0.0015 mol of chrome alum d i f p t dlsestwn adiuvants coating, y g t per 100 grams of mordant and the amount of copolymer for back transfer, sensitornetric test, etc. was completed 'nordant would be 22.0 grams per 100 grams of emulsion as described in the preceding examples. Test results are gelatin. These mordant-chrorne alum mixtures were presented in Table V.

Table V Density Fresh test Coating Metal salt added to mordant Mordant aging Metal salt added to emulsion of resid- No. treatment after mordant ual dye stain Speed Gamma Fog Chrome alum 44 2.30 .01 Chrome alum. g2 Potassi on aluminum r L Potassium aluminum sulfate" .72 133 3. 51 01 39 95 2.91 01 Ferric ammonium sulfateg 3% Cu ri" suliate- Cupric sulfate .62 3o 3. 52 .01

EXAMPLE VI dant companions. After the additions of post digestion adjuvants, and the usual operations of coating, drying, etc., tests for back transfer and sensitometric values were made as previously described. The type of mordant used for each case, the mordant aging treatment and type of hardening agent used, as well as back transfer and sensitometric results are given in Table VI. The fog values reported for the incubated test were determined after subjection to 120 F. and relative humidity for 48 5% aqueous solutions of each of diethylaminoethyl- 20 hours.

Table VI Coat- Density 'Fresh test Incuing 'Mordant Metal salt added to mordant Mordant aging Metal salt added to emulsion of residbated N 0. treatment after mordant ual dye test stain Speed Gamma Fog 1. Copolymer 1 Chrome alum 24 hrs. at 140 F 08 48 3. 21 01 .05 2. o 24 hrs. at 11-.. Chrome alu .83 3.18 .03 13 3- IeZVP 24 hrs.-at 14 F 58 97 3.32 01 .03 4. .AQZVP at 75 F Chrome alum 79 3. 15 03 .04 5 P21 Ie5VP at 140 F 06 13 1. 70 .01 O2 6. P2l1lfe5VP L at 75 F Chrome alum. .18 1 1. 76 01 .02 7- PZMeSVP at. 140 I .43 10 1. 77 01' .01 8. P2Me5VP at 75 F." Ferric ammonium sulf .92 6 1. 58 .01 .01 9 PMe2VP at. 140 F .56 138 3.33 03 .04 10 PMe2Vl? at 75 11--- Potassium aluminum sulfate 1. 48 3. 24 04 .04

1 Diethylaminoethylmethacrylate tertiary salt-diethylaminoethylmethacrylate quaternary salt copolymer.

Poly-l-methyl-2-vinylpyridinium eyclohexanesulionate. 3 Poly-2-methyl-5-vinylpyridine hydrochloride.

methacrylate tertiary salt-diethylaminoethylmethacrylate quaternary salt copolymer mordant, poly-l-methyl-Z- vinylpyridinium cyclohexanesulfonate mordant, and poly- 2-methyl-5-vinylpyridine hydrochloride were prepared. Chrome alum, ferric ammonium sulfate or potassium aluminum sulfate to the extent of 0.041 mol of metal ion per 100 g. of polymer material was added to selected portions of these solutions followed by aging 'of the mordant-metal ion mixtures for 24 hours at F. Duplicate portions of the polymeric solutions were reserved as controls without metal ion admixture and held at 75 F. during the 24 hour aging process of the treated polymer materials. Details of the treatment followed for each case is tabulated in Table Vi. The treated and untreated polymer mordant solutions were then added to equal quantities of a washed positive-type light-sensitive iodobromide gelatin photographic emulsion which had been given a customary second digestion treatment. To those emulsion-mordant mixtures which contained the untreated mordant solutions controls, an amount of chrome alum, ferric ammonium sulfate, or potassium aluminum sulfate, respectively, was added which was equal to the amount of metal ion previously present in each of the respective treated and agedpolymeric morinto six equal portions.

numbered 1 and 6.

EXAMPLE VII portion which served as a control was aged for 24-hours at room temperature of 75 F. At the conclusion of the aging treatment, the six resultant solutions were added to separate identical amounts of a positive-type digested emulsion similar to that described in the preceding examples. Additional chrome alum was then added to emulsion-mordant admixtures containing the first three and the sixth mordant portions so as to bring the total amount of chrome alum to 0.041 mol per 100 grams of vinylpyridine polymer. Emulsion portions numbered 4 and 5 already contained at least this amount of chrome alum introduced via the mordant treatment. After the usual additions of post digestion adjuvants, the six emulsions were coated, dried and tested as described in the previous examples. Test data for the experiment are given in Table VII.

Table VII Mols ch. Idols ch. Fresh test Coating alumllOO g. Mordant aging alum/100 g. Density of Incu- No. mordant treatment mordant to residual bated before emulsion dye stain Speed Gamma Fo test log treatment 24 hrs. at l40 F-.. 0. &1 0. 98 08 3.27 .01 04 .1... 0 0.0342 0.73 97 3. 23 .01 .03 0. 0205 0. 70 103 3. 21 .01 .03 0. 74 106 3. 35 .01 .04 0. 72 l04 3. 20 .01 .04; 0. 0-11 1. 39 100 3. 01 03 .04

EXAMPLE VIII To live equal portions of a 5% aqueous diethylaminoethylrnethacrylate tertiary salt-diethylaminoethylmethacrylate quaternary salt copolyrner mordant solution were added respectively 0.041 mol of chrome alum, 0.0273 mol of potassium aluminum sulfate, 0.082 mol of potassium aluminum sulfate, 0.0273 mol of ferric ammonium sulfate, and 0.082 mol of ferric ammonium sulfate respectively.

then added to each of live equal portions of a digested positive-type silver halide emulsion such as has been described more fully in the preceding examples. The necessary steps for completion of the emulsions and the test operations of the completed films were carried out in a manner analogous to that employed in Example VIII. The results of sensitornetric and back transfer tests are tabulated in Table IX.

Table 1X Density of Fresh test [neu- Coatin Metal salt added per 100 g. moi-dent before Mordant treatment residual bated 0. treatment dye stm'n test Speed Gamma Fog fog 0.041 mol chrome alum 24 hrs. at 140 F 0. 21 100 1.95 .01 01 0.273 mol potassium aluminum sulfated0 0.36 111 1.96 .01 .01 0.082 mol potassium aluminum sulfate do 0.13 111 2. 01 01 .01 0.0273 mol ferric ammonium ul ate (lo 0.19 78 1.76 01 .01 0.082 mol ferric ammonium sulfate do 0. 05 78 1. 66 01 .01

five mordant solutions thus treated were then aged EXAMPLE X These at 140 F. for 24 hours. A sixth control solution of mordant received no additions and was retained at 75 F. for 24 hours. After completion of the aging process, the five treated and the sixth untreated mordant solutions were added to equal portions of a digested positive-type silver halide emulsion as described in the preceding examples. To the sixth control emulsion containing the untreated mordant was then added chrome alum in the amount of 0.041 mol per 100 g. of copolymer mordant. The remaining operations of addition of post digestion adiuvants, coating, drying, etc. were carried out and the usual tests made on the films thus prepared. The results A 5% aqueous solution of diethylaminoethylmethacrylate tertiary salt-diethylaminoethylmethacrylate quaternary salt copolymer mordaut was prepared and divided into six equal portions. To portions numbered 3, 4, 5 and 6 were added respectively 0.0068, 0.0205, 0.041 and 0.0615 mol of chrome alum per 100 g. of copolymer mordant. Portion No. 1 served as a room temperature aged F.) untreated control and portions numbered 2 through 6 were aged at 140 F. for 24 hours. At the conclusion of the aging treatment, the sir. mordant solutions were added to a 5.5 aqueous gelatin solution such F of the tests are given in Table Vill. that each gelatin solution-rnordant admixture contained Table VIII Coat. Density of Fresh test Incuing Metal salt added per 100 g. mordant before Mordant treat- Metal salt added to emulresidual bated No. treatment ment sion per 100 g. mordant dye stain t t 1 Speed Gamma Fog 0.041 mol chrome alum 24 hrs. at 140 F... 0. 08 3. 12 .01 12 0.0273 mol potassium aluminum sulfate"- do 0. 28 102 3. e0 01 .20 0.082 mol potassium aluminum sulfate d 0.19 105 46 01 17 0.0273 mol ferric ammonium sulfate 0. 2g 98 5. 20 .01 13 0.082 mol ferric ammonium sulfate do 0. lo 04 3. 28 01 14 e 0.041 mol chrome alum- 0. 42 3. 41 o1 19 EXAMPLE IX 22.0 g. of niordant per 100 g. of gelating. To each of the gelating solutions containing mordant portions numbered 1, 2, 3 and 4 suflicicnt chrome alum was added to make the concentration 0.041 mol of chrome alum per 100 g. of mordant.

The usual coating aids were added to each of the above six gelatin-mordant compositions and coatings were made from each and dried. Since these coatings were not lightsensitive and contained no silver halide, back transfer tests could be made immediately. '1 he same procedure for back transfer test was followed as was used in the earlier 13 examples, except that the silver halide bearing samples underwent suitable development, fixation, etc., prior to the actual back transfer test operation. The results are shown in Table X.

Table X Mols chrome Mols chrome Coating alum per 100 Mordant aging alum per Density No. g. mordant treatment 100 g. Inorof residbefore treatdant added ual dye ment to mordontstain gelatin admixture 24 hrs. at 75 F 0. 041 .45 24 hrs. at 140 'F 0. 041 .50 d .24 .08 06 .10

EXAMPLE XI Example X was repeated except that the mordant used was poly-1-methyl-2-vinylpyridinium cyclohexane'sulfomate. The results are shown in Tale XI.

Table XI Mols chrome Mols chrome Coating alum per 100 Mordant aging alum per Density No. g. mordant treatment 100 g. morof residbetore treatdant added ual dye merit to mordantstain gelatin admixture 24 hrs. at 75 F u 0. 041 .38 24 hrs. at 140 F O. 041 .36 do 0. 0342 .14

Among the acid dyes which can be mordanted by means of the polymeric mordants having the improved ditlusmg characteristics according to this invention are:

An advantage of the invention is that it provides a new and simple process for reducing the diffusing tendencies of polymeric acid dye mordants useful in dye imbibition and dye transfer printing operations. Premordanted films containing the improved polymeric mordants along with a light-sensitive silver halide may be exposed and processed before dye transfer so that the film will bear records of silver, e.g., an optical sound track.

A further advantage of the invention is that the improved polymeric mordants do not fog silver halide layers and can be incorporated directly therein. A still further advantage is that the improved mordants in the dye imbibition blank or image receiving layer produces dye images of increased sharpness. Another advantage of the invention is that a large number of satisfactory prints can be made from the same matrix in routine dye transfer printing. Yet another advantage is the reduction in objectionable dye density in high light areas of the final print.

An additional advantage of the invention is that it provides improved non-difiusing and non-migrating polymeric acid dye mordants which can be incorporated in light-sensitive silver halide emulsions and in photographic elements containing light-sensitive silver halide without deleterious effect on the photographic properties of the light-sensitive material. Still other advantages will be apparent from the above.

The invention claimed is:

1. The process for reducing in a dye transfer receiving element the back transfer tendencies of a watersoluble, photographic polymeric acid dye mordant selected from the group consisting of (a) vinyl copolymers of monoethylenically unsaturated compounds having tertiary amine salt groups and monoethylenically unsaturated compounds having quaternary ammonium salt groups, (b) vinyl copolymers of said unsaturated compounds with up to 50% by weight of another monoethylenically unsaturated compound, and (c) quaternary salts of polyvinylpyridine, which comprises admimng said mordant in aqueous solution with from 0.006 to 0.085 mol per grams of mordant of polyvalent metal ions selected from the group consisting of chromic, cupric, aluminum and ferric ions, subsequently aging said solution at a temperature of from 45 F. to 212 F. for a period of at least 2 /2 hours, the temperature and time of said aging treatment being selected so that the back transfer tendencies of said mordant are reduced by more than about 40% and coating said aged solution on said dye transfer receiving element.

2. A process as defined in claim 1 wherein said aged solution is impregnated into said dye transfer element.

3. The process set forth in claim 1 wherein the solution is aged at a temperature in the range from 75 F. to F.

4. The process of making a film element comprising admixing in solution (1) a Water-soluble, photographic polymeric acid mordant selected from the group consisting of (a) vinyl copolymers of monoethylenically unsaturated compounds having tertiary amine salt groups and monoethylenically unsaturated compounds having quaternary ammonium salt groups, (.5) vinyl copolymers of said unsaturated compounds with up to 50% by weight of another monoethylenically unsaturated compound, and (c) quaternary salts of polyvinylpyridine, and (2) polyvalent metal ions selected from the group consisting of chromic, cupric, aluminum and ferric ions, aging said solution of mordant and metal ions at a temperature of from 45 F. to 212 F. for a period of at least 2 hours, the temperature and time of said aging treatment being selected so that the back transfer tendencies of said mordant are reduced by more than about 40%, after said aging admixing with said solution a water-permeable colloid to form an emulsion, and coating said emulsion onto a film support.

5. A photographic element comprising a water-permeable colloid emulsion containing a light-sensitive silver halide and mordanting amounts of a solution prepared by admixing in aqueous solution a water-soluble photographic polymeric acid dye mordant selected from the group consisting of (a) vinyl copolymers of monoethylenically unsaturated compounds having tertiary amine salt groups and monoethylenically unsaturated compounds having quaternary ammonium salt groups, (b) vinyl copolymers of said unsaturated compounds with up to 50% by weight of another monoethylenically unsaturated compound, and (c) quaternary salts of polyvinylpyridine, and metal ions in an amount of from 0.006 to 0.085 mol per 100 grams of mordant, said metal ions selected from the group consisting of chromic, cuprie, aluminum and ferric, and subsequently aging said solution at a temperature of from 45 F. to 212 F. for a period of at least 2 /2 hours, the temperature and time of said aging treatment being selected so that the back spanner 1% transfer tendencies of said mordant are reduced by more than about 40% 6. A dye imbibition transfer element comprising a support and a water-permeable colloid layer which coinprises a water-permeable colloid emulsion containing in rnordanting amounts a solution prepared by admixing in aqueous solution a water-soluble photographic polymeric acid dye niordant selected from the group consisting of (a) vinyl copolymers of monoethylenically unsaturated compounds having tertiary amine salt groups and monoethylenically unsaturated compounds having quaternary ammonium salt groups, (b) vinyl copolyrners of said unsaturated compounds with up to 50% by weight of another monoethylenically unsaturated compound, and (c) quaternary salts of polyvinylpyridine, and metal ions in an amount of from 0.006 to 0.085 mol per 100 grains of mordant, said metal ions selected from the group consisting of chromic, cupric, aluminum and ferric, and subsequently aging said solution at a temperature of from 45 F. to 212 F. for a period of at least 2 /2 hours, the temperature and time of said aging treatment being selected so that the back transi'er tendencies of said mordant are reduced by more than about 40%.

References Cited in the file of this patent UNITED STATES PATENTS Dawson ec. 12, Schlack Sept. 17, Russell et al. Sept. 16, Barney June 28, Kern Oct. 24, Hart et al. Oct. 24, Weyerts Apr. 10, Jennings Apr. 21, Carroll et al. Apr. 13, Gray July 3, Russell ()ct. 23, Wesp et al. Nov. 19, Delangre Jan. 28, Gray et al. June 17, Straley et al. Oct. 21, Meader et a]. July 28,

FOREIGN PATENTS Great Britain June 12, Great Britain Mar. 12, 

1. THE PROCESS FOR REDUCING IN A DYE TRANSFER RECEIVING ELEMENT THE BACK TRANSFER TENDENCIES OF A WATERSOLUBLE, PHOTOGRAPHIC POLYMERIC ACID DYE MORDANT SELECTED FROM THE GROUP CONSISTING OF (A) VINYL COPOLYMERS OF MONOETHYLENICALLY UNSATURATED COMPOUNDS HAVING TERTIARY AMINE SALT GROUPS AND MONOETHYLENICALLY UNSATURATED COMPOUNDS HAVING QUATERNARY AMMONIUM SALT GROUPS, (B) VINYL COPOLYMERS OF SAID UNSATURATED COMPOUNDS WITH UP TO 50% BY WEIGHT OF ANOTHER MONOETHYLENICALLY UNSATURATED COMPOUND, AND (C) QUATERNARY SALTS OF POLYINYLPYRIDINE, WHICH COMPRISES ADMIXING SAID MORDANT IN AQUEOUS SOLUTION WITH FROM 0.006 TO 0.085 MOL PER 100 GRAMS OF MORDANT POLYVALENT METAL IONS SELECTED FROM THE GROUP CONSISTING OF CHROMIC, CUPRIC, ALUMINUM AND FERRIC IONS, SUBSEQUENTLY AGING SAID SOLUTION AT A TEMPERATURE OF FROM 45*F. TO 212*F. FOR A PERIOD OF AT LEAST 1 1/2 HOURS, THE TEMPERATURE AND TIME OF SAID AGING TREATMENT BEING SELECTED SO THAT THE BACK TRANSFER TENDENCIES OF SAID MORDANT ARE REDUCED BY MORE THAN ABOUT 40% AND COATING SAID AGED SOLUTION ON SAID DYE TRANSFER RECEIVING ELEMENT. 